DE4233198A1 - Substituted thiophenecarboxamides - Google Patents
Substituted thiophenecarboxamidesInfo
- Publication number
- DE4233198A1 DE4233198A1 DE4233198A DE4233198A DE4233198A1 DE 4233198 A1 DE4233198 A1 DE 4233198A1 DE 4233198 A DE4233198 A DE 4233198A DE 4233198 A DE4233198 A DE 4233198A DE 4233198 A1 DE4233198 A1 DE 4233198A1
- Authority
- DE
- Germany
- Prior art keywords
- methoxy
- carboxylic acid
- amide
- dibromothiophene
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- DENPQNAWGQXKCU-UHFFFAOYSA-N thiophene-2-carboxamide Chemical class NC(=O)C1=CC=CS1 DENPQNAWGQXKCU-UHFFFAOYSA-N 0.000 title claims description 17
- -1 cyano, nitro, methyl Chemical group 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- ZLWLKVQCHZSSEL-UHFFFAOYSA-N 4,5-dibromo-n-(4-bromophenyl)thiophene-2-carboxamide Chemical compound S1C(Br)=C(Br)C=C1C(=O)NC1=CC=C(Br)C=C1 ZLWLKVQCHZSSEL-UHFFFAOYSA-N 0.000 claims description 12
- RFMFVMZSMIPYAA-UHFFFAOYSA-N 4,5-dibromo-n-(2,3-dichlorophenyl)thiophene-2-carboxamide Chemical compound ClC1=CC=CC(NC(=O)C=2SC(Br)=C(Br)C=2)=C1Cl RFMFVMZSMIPYAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- WTJNKJXMQNZRFV-UHFFFAOYSA-N 4,5-dibromo-n-[2-(3,4-dimethoxyphenyl)ethyl]thiophene-2-carboxamide Chemical compound C1=C(OC)C(OC)=CC=C1CCNC(=O)C1=CC(Br)=C(Br)S1 WTJNKJXMQNZRFV-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 241000607479 Yersinia pestis Species 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 claims description 2
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 claims description 2
- 125000004441 haloalkylsulfonyl group Chemical group 0.000 claims description 2
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 2
- YNSCKPCDFIDINW-UHFFFAOYSA-N 3-[[2-[[1-[2-(dimethylamino)acetyl]-6-methoxy-4,4-dimethyl-2,3-dihydroquinolin-7-yl]amino]-7h-pyrrolo[2,3-d]pyrimidin-4-yl]amino]thiophene-2-carboxamide Chemical class COC1=CC(C(CCN2C(=O)CN(C)C)(C)C)=C2C=C1NC(N=C1NC=CC1=1)=NC=1NC=1C=CSC=1C(N)=O YNSCKPCDFIDINW-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000004480 active ingredient Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- USFXRYVNRUMABJ-UHFFFAOYSA-N 4,5-dibromothiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC(Br)=C(Br)S1 USFXRYVNRUMABJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- 241001330975 Magnaporthe oryzae Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- GHTYWAJRIXJGMS-UHFFFAOYSA-N 4,5-dibromothiophene-2-carbonyl chloride Chemical compound ClC(=O)C1=CC(Br)=C(Br)S1 GHTYWAJRIXJGMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000371644 Curvularia ravenelii Species 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- 241001281802 Pseudoperonospora Species 0.000 description 1
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 1
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- 241000221300 Puccinia Species 0.000 description 1
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- 241000228454 Pyrenophora graminea Species 0.000 description 1
- 241000520648 Pyrenophora teres Species 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 241000918584 Pythium ultimum Species 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241001533598 Septoria Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 1
- 241001617088 Thanatephorus sasakii Species 0.000 description 1
- 241000722133 Tilletia Species 0.000 description 1
- 241000722093 Tilletia caries Species 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OUYSIVYIKXCLTF-UHFFFAOYSA-N [C].S1C=CC=C1 Chemical class [C].S1C=CC=C1 OUYSIVYIKXCLTF-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- BLHUAXIDWCQEPL-UHFFFAOYSA-M dibenzyl(dimethyl)azanium;methyl sulfate Chemical compound COS([O-])(=O)=O.C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 BLHUAXIDWCQEPL-UHFFFAOYSA-M 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229940042880 natural phospholipid Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
Die Erfindung betrifft neue substituierte Thiophencarbonsäureamide, ein Verfahren zu ihrer Herstellung und ihre Verwendung in Schädlingsbekämpfungsmitteln.The invention relates to new substituted thiophenecarboxamides, a process for their manufacture and their use in pesticides.
Es ist bekannt, daß bestimmte Thiophencarbonsäureamid-Derivate wie beispielsweise die Verbindung 3-Chlor-N-(1 -phenylethyl)-benzothiophen-2-carbox amid-S,S-dioxid fungizide Eigenschaften besitzen (vergl. z. B. DE-OS 38 32 848).It is known that certain thiophenecarboxamide derivatives such as for example the compound 3-chloro-N- (1-phenylethyl) benzothiophene-2-carbox amide-S, S-dioxide have fungicidal properties (see, for example, DE-OS 38 32 848).
Die Wirksamkeit dieser vorbekannten Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht in allen Anwendungsgebieten völlig zufriedenstellend.The effectiveness of these previously known compounds is, however, in particular low application rates and concentrations not in all areas of application completely satisfactory.
Weiterhin sind bestimmte substituierte Thiophencarbonsäureamide, wie beispielweise die Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-bromphe nyl)-amid (CA-Reg. No. 15686-72-3), 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3- dichlorphenyl)-amid (CA-Reg. No. 15950-37-5) und 4,5-Dibrom-thiophen-2- carbonsäure-N-[2-(3,4-dimethoxyphenyl)-ethyl]-amid (CA-Reg. No. 98215-50-0) bekannt (vergl. z. B. US-PS 3.303.201; OB 10 85 974; J. Chem. Soc. Perkin Trans. I, 275-281 [1985]). Über eine fungizide Wirksamkeit dieser Verbindungen ist bisher nichts bekannt. Furthermore, certain substituted thiophenecarboxamides, such as for example the compounds 4,5-dibromothiophene-2-carboxylic acid N- (4-bromophe nyl) -amide (CA-Reg. No. 15686-72-3), 4,5-dibromothiophene-2-carboxylic acid N- (2,3- dichlorophenyl) -amide (CA-Reg. No. 15950-37-5) and 4,5-dibromo-thiophene-2- carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide (CA Reg. No. 98215-50-0) known (see, for example, US Pat. No. 3,303,201; OB 10 85 974; J. Chem. Soc. Perkin Trans. I, 275-281 [1985]). So far there has been no fungicidal activity of these compounds nothing known.
Es wurden neue substituierte Thiophencarbonsäureamide der allgemeinen Formel (I),New substituted thiophenecarboxamides of the general formula (I)
in welcher
R für Wasserstoff oder Alkyl steht,
A für zweifach verknüpftes Alkandiyl steht,
Ar für gegebenenfalls substituiertes Aryl steht und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom
phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-ainid und
4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphenyl)ethyl]-a-mid,
gefunden.in which
R represents hydrogen or alkyl,
A represents double-linked alkanediyl,
Ar represents optionally substituted aryl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromothiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -ainide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] -a-mid.
Die Verbindungen der Formel (I) können gegebenenfalls in Abhängigkeit von der Art der Substituenten als geometrische und/oder optische Isomere oder Isomerenge mische unterschiedlicher Zusammensetzung vorliegen. Sowohl die reinen Isomeren als auch die Isomerengemische werden erfindungsgemäß beansprucht.The compounds of formula (I) may optionally, depending on the Type of the substituents as geometric and / or optical isomers or isomer set Mixtures of different compositions are present. Both the pure isomers as well as the isomer mixtures are claimed according to the invention.
Weiterhin wurde gefunden daß man die neuen substituierten Thiophencarbonsäure amide der allgemeinen Formel (I),It was also found that the new substituted thiophene carboxylic acid amides of the general formula (I),
in welcher
R für Wasserstoff oder Alkyl steht,
A für zweifach verknüpftes Alkandiyl steht,
Ar für gegebenenfalls substituiertes Aryl steht und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom
phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-amid und
4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphenyl)-ethyl]--amid
erhält, wenn man Thiophencarbonsäurehalogenide der Formel (II),in which
R represents hydrogen or alkyl,
A represents double-linked alkanediyl,
Ar represents optionally substituted aryl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromo-thiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide, if thiophenecarboxylic acid halides of the formula (II) are obtained,
in welcher
Hal für Halogen steht,
mit Aminen der Formel (III),in which
Hal stands for halogen,
with amines of the formula (III),
R-NH-(A)n-Ar (III)R-NH- (A) n -Ar (III)
in welcher
R, A, Ar und n die oben angegebene Bedeutung haben,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Ge
genwart eines Reaktionshilfsmittels umsetzt.
in which
R, A, Ar and n have the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.
Schließlich wurde gefunden, daß die neuen substituierten Thiophencarbon säureamide der allgemeinen Formel (I) gute Wirksamkeit gegenüber Schädlingen besitzen.Finally, it was found that the new substituted thiophene carbon Acid amides of the general formula (I) have good activity against pests have.
Überraschenderweise zeigen die erfindungsgemäßen substituierten Thiophencarbon säureamide der allgemeinen Formel (I) eine erheblich bessere Wirksamkeit gegenüber pflanzenschädigenden Mikroorganismen im Vergleich zu den aus dem Stand der Technik bekannten Thiophencarbonsäureamid-Derivaten, wie beispiels weise die Verbindung 3-Chlor-N-(1-phenylethyl)-benzothiophen-2-carboxamid-S,S- dioxid, welches chemisch und/oder wirkungsmäßig naheliegende Verbindungen sind.The substituted thiophene carbon according to the invention surprisingly show acid amides of the general formula (I) have a considerably better activity against plant-damaging microorganisms compared to those from the State of the art thiophenecarboxamide derivatives, such as the compound 3-chloro-N- (1-phenylethyl) -benzothiophene-2-carboxamide-S, S- dioxide, which are chemically and / or functionally obvious compounds.
R steht für geradkettiges oder verzweigtes Alkyl; vorzugsweise für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Kohlenstoffatomen; besonders bevorzugt mit 1 bis 4 Kohlenstoffatomen.R represents straight-chain or branched alkyl; preferably for straight chain or branched alkyl having 1 to 8 carbon atoms; particularly preferred with 1 to 4 carbon atoms.
A steht für zweifach verknüpftes Alkandiyl; vorzugsweise für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 8 Kohlenstoffatomen; besonders bevorzugt für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 4 Kohlenstoffatomen.A stands for double linked alkanediyl; preferably for straight chain or branched, double-linked alkanediyl having 1 to 8 carbon atoms; particularly preferred for straight-chain or branched, double-linked Alkanediyl with 1 to 4 carbon atoms.
Ar steht für gegebenenfalls ein- bis mehrfach, gleich oder verschieden substi tuiertes Phenyl, vorzugsweise für unsubstituiertes oder ein- bis fünffach, gleich oder verschieden substituiertes Phenyl; besonders bevorzugt für unsubsti tuiertes oder ein- bis dreifach, gleich oder verschieden substituiertes Phenyl.Ar stands for one or more, optionally, the same or different substances tuated phenyl, preferably for unsubstituted or one to five times the same or differently substituted phenyl; particularly preferred for unsubsti tuated or mono- to trisubstituted, identically or differently substituted phenyl.
Ar steht auch für Naphthyl.Ar also stands for naphthyl.
Die erfindungsgemäßen substituierten Thiophencarbonsäureamide sind durch die
Formel (I) allgemein definiert. Bevorzugt sind Verbindungen der Formel (I), bei
welchen
R für Wasserstoff oder für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Koh
lenstoffatomen steht,
A für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 8
Kohlenstoffatomen steht,
Ar für gegebenenfalls einfach bis mehrfach, gleich oder verschieden substituiertes
Phenyl steht, wobei als Substituenten in Frage kommen:
Halogen, Cyano, Nitro, jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy,
Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 4 Kohlenstoffato
men, jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy,
Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils
1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogen
atomen, jeweils geradkettiges oder verzweigtes Alkoxycarbonyl oder Alkox
iminoalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen
Halogen, geradkettiges oder verzweigtes Alkyl, geradkettiges oder verzweigtes
Alkoxy, geradkettiges oder verzweigtes Halogenalkyl und geradkettiges oder
verzweigtes Halogenalkoxy mit jeweils 1 bis 4 Kohlenstoffatomen und gegebe
nenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen substituiertes
Phenyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom
phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-amid und
4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4dimethoxyphenyl)ethyl]-am-id.The substituted thiophenecarboxamides according to the invention are generally defined by the formula (I). Compounds of formula (I) are preferred in which
R represents hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms,
A represents straight-chain or branched, double-linked alkanediyl having 1 to 8 carbon atoms,
Ar represents phenyl which is monosubstituted to polysubstituted by identical or different substituents, the following being suitable as substituents:
Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 same or different halogen atoms, each straight-chain or branched alkoxycarbonyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts halogen, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain or branched haloalkyl and straight-chain or branched haloalkoxy, each with 1 to 4 Carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted phenyl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromo-thiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4dimethoxyphenyl) ethyl] amid.
Besonders bevorzugt sind Verbindungen der Formel (I), bei welchen
R für Wasserstoff oder für geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Koh
lenstoffatomen steht,
A für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 4
Kohlenstoffatomen steht,
Ar für gegebenenfalls einfach bis fünffach oder ein- bis dreifach, gleich oder
verschieden substituiertes Phenyl steht, wobei als Substituenten in Frage
kommen:
Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s-
oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Me
thylthio, Ethylthio, Methylsulflnyl, Ethylsulfinyl, Methylsulfonyl, Ethyl
sulfonyl, Trifluormethyl, Difluormethyl, Trifluormethoxy, Difluormethoxy,
Trifluormethylthio, Trifluormethylsulfinyl, Trifluormethylsulfonyl, Methoxy
carbonyl, Ethoxycarbonyl, Methoximinomethyl, Methoximinoethyl, Ethoximi
nomethyl, Ethoximinoethyl oder gegebenenfalls ein- bis dreifach, gleich oder
verschieden durch Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl,
Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy substituiertes Phe
nyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom
phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-amid und
4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphenyl)-ethyl]--amid.Compounds of the formula (I) in which
R represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
A represents straight-chain or branched, double-linked alkanediyl having 1 to 4 carbon atoms,
Ar represents phenyl which is monosubstituted to pentasupon or monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents:
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- , s- or t-butoxy, Me methylthio, ethylthio, Methylsulflnyl, ethylsulfinyl, methylsulfonyl, ethyl sulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, methoxy carbonyl, ethoxycarbonyl, methoximinomethyl, methoximinoethyl, Ethoximi nomethyl, ethoximinoethyl or optionally phenyl and trisubstituted, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromo-thiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide.
Ganz besonders bevorzugt sind Verbindungen der Formel (I), bei welchen
R für Wasserstoff oder Methyl steht,
A für zweifach verknüpftes Methylen oder Ethylen steht,
Ar für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes
Phenyl steht, wobei als Substituenten in Frage kommen:
Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Methylthio, Methyl
sulfonyl, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Trifluormethyl
sulfonyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom
phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-amid und
4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphenyl)ethyl]-a-mid.
Compounds of the formula (I) in which
R represents hydrogen or methyl,
A represents doubly linked methylene or ethylene,
Ar represents phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents:
Fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, methyl sulfonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethyl sulfonyl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromo-thiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] -a-mid.
Im einzelnen seien die bei den Herstellungsbeispielen aufgeführten Verbindungen der allgemeinen Formel (I) genannt.In particular, the compounds listed in the preparation examples of the general formula (I).
Verwendet man beispielsweise 4,5-Dibrom-thiophen-2-carbonsäurechlorid und 3,4- Dimethylanilin als Ausgangsverbindungen, so läßt sich der Reaktionsablauf des er findungsgemäßen Verfahrens durch das folgende Formelschema darstellen:If, for example, 4,5-dibromothiophene-2-carboxylic acid chloride and 3,4- Dimethylaniline as starting compounds, so he can the course of the reaction represent the inventive method by the following formula:
Die zur Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe benötigten Thiophencarbonsäurehalogenide sind durch die Formel (II) allgemein definiert. In dieser Formel (II) steht Hal vorzugsweise für Chlor oder Brom.To carry out the process according to the invention as starting materials required thiophene carboxylic acid halides are general by the formula (II) Are defined. In this formula (II), Hal preferably represents chlorine or bromine.
Die Thiophencarbonsäurehalogenide der Formel (II) sind bekannt (vergl. z. B. EP 450 355; US-PS 3.303.201; DE 12 01 952; GB 10 85 974).The thiophene carboxylic acid halides of the formula (II) are known (cf., for example, EP 450 355; U.S. Patent 3,303,201; DE 12 01 952; GB 10 85 974).
Die zur Durchführung des erfindungsgemäßen Verfahrens weiterhin als Aus gangsstoffe benötigten Amine sind durch die Formel (III) allgemein definiert. In dieser Formel (III) stehen R, A, Ar und n vorzugsweise für diejenigen Reste und Indices, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt für diese Substituenten und diese Indexzahl genannt wurden. The to carry out the method according to the invention as an off Amines required starting materials are generally defined by the formula (III). In of this formula (III) R, A, Ar and n preferably represent those radicals and Indices already in connection with the description of the invention Compounds of formula (I) as preferred for these substituents and these Index number.
Die Amine der Formel (III) sind allgemein bekannte Verbindungen der organischen Chemie oder erhältlich in Analogie zu allgemein bekannten Verfahren.The amines of the formula (III) are generally known compounds of the organic Chemistry or available in analogy to generally known methods.
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kom men inerte organische Lösungsmittel in Frage. Hierzu gehören insbesondere aliphati sche, alicyclische oder aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Pe trolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff; Ether, wie Diethylether, Diisopropylether, Dioxan, Tetrahydrofuran oder Ethylen glykoldimethyl- oder -diethylether; Ketone, wie Aceton, Butanon oder Methyl isobutyl-keton; Nitrile, wie Acetonitril, Propionitril oder Benzonitril; Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N-Methylformanilid, N-Methyl pyrrolidon oder Hexamethylphosphorsäuretriamid; Ester wie Essigsäuremethylester oder Essigsäureethylester oder Sulfoxide, wie Dimethylsulfoxid.Coming as a diluent for carrying out the process according to the invention inert organic solvents. These include in particular aliphati cal, alicyclic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, Pe trole ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides like N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate or sulfoxides, such as dimethyl sulfoxide.
Das erfindungsgemäße Verfahren wird vorzugsweise in Gegenwart eines geeigneten Reaktionshilfsmittels durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen in Frage. Hierzu gehören beispielsweise Erdalkali- oder Alka limetallhydride, -hydroxide, -amide, -alkoholate, -acetate, -carbonate oder -hydro gencarbonate, wie beispielsweise Natriumhydrid, Natriumamid, Natriummethylat, Natriumethylat, Kalium-tert-butylat, Natriumhydroxid, Kaliumhydroxid, Ammoni umhydroxid, Natriumacetat, Kaliumacetat, Calciumacetat, Ammoniumacetat, Natri umcarbonat, Kaliumcarbonat, Kaliumhydrogencarbonat, Natriumhydrogencarbonat oder Ammoniumcarbonat sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tributylamin, N,N-Dimethylanilin, Pyridin, N-Methylpiperidin, N,N-Dimethylami nopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabi cycloundecen (DBU).The process according to the invention is preferably carried out in the presence of a suitable one Reaction auxiliary carried out. All the usual inorganic ones come as such or organic bases in question. These include, for example, alkaline earth or alka limetal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydro gene carbonates, such as sodium hydride, sodium amide, sodium methylate, Sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonia umhydroxid, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, natri umcarbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines, such as trimethylamine, triethylamine, Tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylami nopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabi cycloundecene (DBU).
Das erfindungsgemäße Verfahren kann gegebenenfalls auch in einem Zweiphasensy stem, wie beispielsweise Wasser/Toluol oder Wasser/Dichlormethan, gegebenenfalls in Gegenwart eines geeigneten Phasentransferkatalysators, durchgeführt werden. Als Beispiele für solche Katalysatoren seien genannt: Tetrabutylammoniumiodid, Tetra butylammoniumbromid, Tetrabutylammoniumchlorid, Tributyl-methylphosphoni umbromid, Trimethyl C13/C15-alkylammoniumchlorid, Trimethyl-C 13/C15-alkyl ammoniumbromid, Dibenzyl-dimethyl-ammoniummethylsulfat, Dimethyl-C12/C14- alkyl-benzylammoniumchlorid, Dimethyl-C12/C14-alkyl-benzylammoniumbromid, Tetrabutylammoniumhydroxid, Triethylbenzylammoniumchlorid, Methyltrioctylam moniumchlorid, Trimethylbenzylammoniumchlorid, 15-Krone-5, 18-Krone-6 oder Tris-[2-(2-methoxyethoxy)-ethyl]-amin.If appropriate, the process according to the invention can also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. As examples of such catalysts may be mentioned are: tetrabutylammonium iodide, tetra butylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphoni bromide, trimethyl C 13 / C 15 -alkylammoniumchlorid, trimethyl-C 13 / C 15 alkyl ammonium bromide, dibenzyl dimethyl ammonium methyl sulfate, dimethyl-C12 / C 14 - alkyl-benzylammonium chloride, dimethyl-C 12 / C 14 -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylam monium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2-methoxyethoxy ) ethyl] amine.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20°C und 150°C, vorzugsweise bei Temperaturen zwi schen 0°C und 120°C.The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied over a wide range. Generally you work at temperatures between -20 ° C and 150 ° C, preferably at temperatures between between 0 ° C and 120 ° C.
Das erfindungsgemäße Verfahren wird üblicherweise unter Normaldruck durchge führt. Es ist jedoch auch möglich unter erhöhtem oder vermindertem Druck zu arbei ten.The process according to the invention is usually carried out under normal pressure leads. However, it is also possible to work under increased or reduced pressure ten.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol an Thio phencarbonsäurehalogenid der Formel (II) im allgemeinen 1,0 bis 5,0 Mol, vorzugs weise 1,0 bis 2,5 Mol an Amin der Formel (III) und gegebenenfalls 1,0 bis 5,0 Mol, vorzugsweise 1,0 bis 2,5 Mol an als Reaktionshilfsmittel verwendeter Base ein. Die Reaktionsdurchführung, Aufarbeitung und Isolierung der Reaktionsprodukte erfolgt nach allgemein bekannten Verfahren (vergl. hierzu auch die Herstellungsbeispiele).To carry out the process according to the invention, thio is employed per mole phencarboxylic acid halide of the formula (II) in general 1.0 to 5.0 mol, preferably example 1.0 to 2.5 mol of amine of the formula (III) and optionally 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol of base used as reaction auxiliary. The The reaction is carried out, worked up and isolated from the reaction products according to generally known methods (see also the production examples).
Die Reinigung der Endprodukte der Formel (I) erfolgt mit Hilfe üblicher Verfahren, beispielsweise durch Säulenchromatographie oder durch Umkristallisieren.The end products of the formula (I) are purified using customary processes, for example by column chromatography or by recrystallization.
Die Charakterisierung erfolgt mit Hilfe des Schmelzpunktes oder bei nicht kristallisierenden Verbindungen mit Hilfe des Brechungsindex oder der Protonen- Kernresonanzspektroskopie (1H-NMR).The characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy ( 1 H-NMR).
Die erfindungsgemäßen Wirkstoffe weisen eine starke Wirkung gegen Schädlinge auf und können zur Bekämpfung von unerwünschten Schadorganismen praktisch eingesetzt werden. Die Wirkstoffe sind für den Gebrauch als Pflanzenschutzmittel, insbesondere als Fungizide geeignet. The active compounds according to the invention have a strong action against pests on and can be practical to combat unwanted pests be used. The active ingredients are for use as pesticides, particularly suitable as fungicides.
Fungizide Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, Deuteromycetes.Fungicides in crop protection are used to combat plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen Krankheiten,
die unter die oben aufgezählten Oberbegriffe fallen, genannt:
Pythium-Arten, wie beispielsweise Pythium ultimum;
Phytophthora-Arten, wie beispielsweise Phytophthora infestans;
Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oder Pseu
doperonospora cubensis;
Plasmopara-Arten, wie beispielsweise Plasmopara viticola;
Peronospora-Arten, wie beispielsweise Peronospora pisi oder Peronospora brassicae;
Erysiphe-Arten, wie beispielsweise Erysiphe graminis;
Sphaerotheca-Arten, wie beispielsweise Sphaerotheca fuliginea;
Podosphaera-Arten, wie beispielsweise Podosphaera leucotricha;
Venturia-Arten, wie beispielsweise Venturia inaequalis;
Pyrenophora-Arten, wie beispielweise Pyrenophora teres oder Pyrenophora graminea
(Konidienform: Drechslera, Synonym: Helminthosporium);
Cochliobolus-Arten, wie beispielsweise Cochliobolus sativus (Konidienform:
Drechslera, Synonym: Helminthosporium);
Uromyces-Arten, wie beispielsweise Uromyces appendiculatus;
Puccinia-Arten, wie beispielsweise Puccinia recondita;
Tilletia-Arten, wie beispielsweise Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii;
Pyricularia-Arten, wie beispielsweise Pyricularia oryzae;
Fusarium-Arten, wie beispielsweise Fusarium culmorum;
Botrytis-Arten, wie beispielsweise Botrytis cinerea;
Septoria-Arten, wie beispielsweise Septoria nodorum;
Leptosphaeria-Arten, wie beispielsweise Leptosphaeria nodorum;
Cercospora-Arten, wie beispielsweise Cercospora canescens;
Alternaria-Arten, wie beispielsweise Altemaria brassicae;
Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporeila herpotrichoides.
Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseu doperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Altemaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporeila herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflan zenkranheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdi schen Pflanzenteilen, von Pflanz- und Saatgut und des Bodens.The good plant tolerance of the active ingredients in the control of the plant Concentrations necessary for critical diseases allow treatment of above ground parts of plants, plant and seed and soil.
Dabei können die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Krankheiten im Obst- und Gemüseanbau, wie beispielsweise gegen den Erreger des echten Apfelmehltaus (Podosphaera leucotricha) oder zur Bekämpfung von Reiskrankheiten, wie beispielsweise gegen den Erreger der Reisfleckenkrankheit (Pyricularia oryzae) eingesetzt werden. Daneben besitzen die erfindungsgemäßen Wirkstoffe auch eine resistenz-induzierende Wirksamkeit Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und -Warmnebel-Formulierungen.The active compounds according to the invention can be used with particularly good success Combating diseases in fruit and vegetable growing, such as against the pathogen of the real powdery mildew (Podosphaera leucotricha) or Combating rice diseases, such as against the pathogen of the Rice spot disease (Pyricularia oryzae) can be used. They also have Active substances according to the invention also have a resistance-inducing activity The active ingredients can depend on their respective physical and / or chemical properties are converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, Aerosols, ultra-fine encapsulations in polymeric substances and in coating compositions for Seeds, as well as ULV cold and warm mist formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid oder Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen in Frage: z. B. natürliche Gesteins mehle, wie Kaoline, Tonerden, Talkum, Kreide, Quartz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: z. B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z. B. nicht ionogene und anionische Emulgatoren, wie Polyoxyethy len-Fettsäureester, Polyoxyethylen-Fettalkohol-Ether, z. B. Alkylarylpolyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergier mittel kommen in Frage: z. B. Ligninsulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of using Water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons, such as Cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as Dimethylformamide or dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant such liquids which are gaseous at normal temperature and pressure, e.g. B. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: B. natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, Alumina and silicates; as solid carriers for granules are: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules from inorganic and organic Flours and granules made of organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethy len fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a disperser middle come into question: z. B. Ligninsulfitablaugen and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische, pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic, powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z. B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90%.The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen, wie Fungizide, Insektizide, Akarizide und Herbizide sowie in Mischungen mit Düngemitteln und Wachstumsregulatoren.The active compounds according to the invention can be mixed with in the formulations other known active ingredients are present, such as fungicides, insecticides, acaricides and Herbicides and in mixtures with fertilizers and growth regulators.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus be reiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Spritz pulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z. B. durch Gießen, Verspritzen, Versprühen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low-Volume-Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.The active substances can be used as such, in the form of their formulations or in the form thereof rode application forms, such as ready-made solutions, suspensions, spray powders, pastes, soluble powders, dusts and granules can be used. The Application happens in the usual way, e.g. B. by pouring, spraying, Spraying, scattering, dusting, foaming, brushing, etc. It is further possible to apply the active ingredients using the ultra-low-volume process or to inject the active substance preparation or the active substance itself into the soil. It the seeds of the plants can also be treated.
Bei der Behandlung von Pflanzenteilen können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden: Sie liegen im allge meinen zwischen 1 und 0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 Gew.-%.In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area: They are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.
Bei der Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 Gew.-% am Wirkungsort erforderlich.In the treatment of the soil, active ingredient concentrations of 0.00001 to 0.1% by weight are preferably from 0.0001 to 0.02% by weight required at the site of action.
Zu 2,0 g (0,02 Mol) Triethylamin und 2,4 g (0,02 Mol) 3,4-Dimethylanilin in 30 ml Toluol gibt man bei Raumtemperatur unter Rühren eine Lösung von 6,0 g (0,02 Mol) 4,5-Dibromthiophen-2-carbonsäurechlorid zu, erwärmt anschließend für 2 Stunden auf 50°C. Zur Aufarbeitung kühlt man den Reaktionsansatz auf Raumtemperatur ab, gibt die Mischung in Wasser, saugt ausgefallenen Feststoff ab, wäscht nach mit Wasser und n-Hexan und trocknet den Rückstand im Vakuum bei 50°C.To 2.0 g (0.02 mol) of triethylamine and 2.4 g (0.02 mol) of 3,4-dimethylaniline in 30 ml A solution of 6.0 g (0.02 Mol) 4,5-dibromothiophene-2-carboxylic acid chloride, then heated for 2 Hours at 50 ° C. For working up, the reaction mixture is cooled Room temperature, gives the mixture in water, sucks out precipitated solid, washes with water and n-hexane and dries the residue in vacuo 50 ° C.
Man erhält 6,4 g (82% der Theorie) an 4,5-Dibromthiophen-2-carbonsäure-N-(3,4- dimethylphenyl)-amid vom Schmelzpunkt 216-217°C. 6.4 g (82% of theory) of 4,5-dibromothiophene-2-carboxylic acid N- (3,4- dimethylphenyl) amide melting point 216-217 ° C.
In entsprechender Weise und gemäß den allgemeinen Angaben zur Herstellung erhält man die folgenden substituierten Thiophencarbonsäureamide der allgemeinen Formel (I):In a corresponding manner and in accordance with the general information on the manufacture the following substituted thiophenecarboxamides of the general Formula (I):
In den folgenden Anwendungsbeispielen wurde die nachstehend aufgeführte Verbin dung als Vergleichssubstanz eingesetzt:In the following application examples, the verb below was used used as a reference substance:
3-Chlor-N-(1-phenylethyl)-benzothiophen-2-carboxamid-S,S-dioxid (bekannt aus DE-OS 38 32 848). 3-chloro-N- (1-phenylethyl) benzothiophene-2-carboxamide-S, S-dioxide (known from DE-OS 38 32 848).
Pyricularia Test (Reis)/protektiv
Lösungsmittel: 12,5 Gewichtsteile Aceton
Emulgator: 0,3 Gewichtsteile Alkyl-aryl-polyglykolether.Pyricularia test (rice) / protective
Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether.
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man ein Ge wichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und verdünnt das Konzentrat mit Wasser und der angegebenen Menge Emulgator auf die gewünschte Konzentration.A Ge is mixed to produce a suitable preparation of active compound most of the active ingredient with the specified amounts of solvent and dilutes the Concentrate with water and the specified amount of emulsifier to the desired Concentration.
Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Reispflanzen mit der Wirkstoffzubereitung bis zur Tropfnässe. Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer wäßrigen Sporensuspension von Pyricularia oryzae inokuliert.To test for protective effectiveness, young rice plants are sprayed with the Active ingredient preparation to dripping wet. After the spray coating has dried on the plants with an aqueous spore suspension of Pyricularia oryzae inoculated.
Die Pflanzen werden anschließend im Gewächshaus bei 25°C und einer relativen Luftfeuchtigkeit von 100% aufgestellt.The plants are then in a greenhouse at 25 ° C and a relative 100% humidity set up.
4 Tage nach der Inokulation erfolgt die Auswertung des Krankheitsbefalls.The disease infestation is evaluated 4 days after the inoculation.
Bei einer Wirkstoffkonzentration von 0,025% zeigen die Verbindungen einen Wirkungsgrad zwischen 90 und 95% gegenüber der unbehandelten Kontrolle.At an active ingredient concentration of 0.025%, the compounds show one Efficiency between 90 and 95% compared to the untreated control.
Claims (9)
R für Wasserstoff oder Alkyl steht,
A für zweifach verknüpftes Alkandiyl steht,
Ar für gegebenenfalls substituiertes Aryl steht und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4- bromphenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphe nyl)-amid und 4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphe nyl)-ethyl]-amid.1. Substituted thiophenecarboxamides of the general formula (I), in which
R represents hydrogen or alkyl,
A represents double-linked alkanediyl,
Ar represents optionally substituted aryl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromothiophene-2-carboxylic acid N- (4-bromophenyl) amide, 4,5-dibromothiophene-2-carboxylic acid N- (2,3-dichlorophenyl) amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide.
R für Wasserstoff oder für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Kohlenstoffatomen steht,
A für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 8 Kohlenstoffatomen steht,
Ar für gegebenenfalls einfach bis mehrfach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten in Frage kommen:
Halogen, Cyano, Nitro, jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 4 Kohlenstoffatomen, jeweils geradkettiges oder verzweigtes Halogenal kyl, Halogenalkoxy, Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen, jeweils geradkettiges oder verzweigtes Alkoxycarbonyl oder Alkoximinoalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen sowie gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen, geradket tiges oder verzweigtes Alkyl, geradkettiges oder verzweigtes Alkoxy, ge radkettiges oder verzweigtes Halogenalkyl und geradkettiges oder ver zweigtes Halogenalkoxy mit jeweils 1 bis 4 Kohlenstoffatomen und ge gebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen substi tuiertes Phenyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4- bromphenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphe nyl)-amid und 4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphe nyl)-ethyl]-amid.2. thiophenecarboxamides according to claim 1 of formula (I), in which
R represents hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms,
A represents straight-chain or branched, double-linked alkanediyl having 1 to 8 carbon atoms,
Ar represents phenyl which is monosubstituted to polysubstituted by identical or different substituents, the following being suitable as substituents:
Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 the same or different halogen atoms, in each case straight-chain or branched alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and, if appropriate, singly or repeatedly, identically or differently by halogen, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain or branched haloalkyl and straight-chain or branched haloalkoxy each having 1 to 4 carbon atoms and, if appropriate, 1 to 9 identical or different halogen atoms, substituted phenyl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromothiophene-2-carboxylic acid N- (4-bromophenyl) amide, 4,5-dibromothiophene-2-carboxylic acid N- (2,3-dichlorophenyl) amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide.
R für Wasserstoff oder für geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen steht,
A für geradkettiges oder verzweigtes, zweifach verknüpftes Alkandiyl mit 1 bis 4 Kohlenstoffatomen steht,
Ar für gegebenenfalls einfach bis fünffach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten in Frage kommen:
Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-But oxy, Methylthio, Ethylthio, Methylsulfinyl, Ethylsulfinyl, Methyl sulfonyl, Ethylsulfonyl, Trifluormethyl, Difluormethyl, Trifluormethoxy, Difluormethoxy, Trifluormethylthio, Trifluormethylsulfinyl, Trifluorme thylsulfonyl, Methoxycarbonyl, Ethoxycarbonyl, Methoximinomethyl, Methoximinoethyl, Ethoximinomethyl, Ethoximinoethyl oder gegebe nenfalls ein- bis dreifach, gleich oder verschieden durch Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy substituiertes Phenyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4- bromphenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphe nyl)-amid und 4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphe nyl)ethyl]-amid.4. thiophenecarboxamides according to claim 1 of formula (I), in which
R represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
A represents straight-chain or branched, double-linked alkanediyl having 1 to 4 carbon atoms,
Ar represents phenyl which is optionally monosubstituted to pentasubstituted by identical or different substituents, the following being suitable as substituents:
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- , s- or t-but oxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethyl, carbonyl, methoxyethyl, methyloxyethyl, methyloxyethyl, methyloxyethyl, methyloxyethyl, methyloxyethyl, methoxy, methoxy, methoxy, methyloxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methyl, methoxy, methyl, methoxy, methyl, methoxy, methyl, methyl, methyl optionally mono- to trisubstituted, identical or different by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromothiophene-2-carboxylic acid N- (4-bromophenyl) amide, 4,5-dibromothiophene-2-carboxylic acid N- (2,3-dichlorophenyl) amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide.
R für Wasserstoff oder Methyl steht,
A für zweifach verknüpftes Methylen oder Ethylen steht,
Ar für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten in Frage kommen:
Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Methylthio, Methylsulfonyl, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Trifluormethylsulfonyl und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4- bromphenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphe nyl)-amid und 4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphe nyl)ethyl]-amid.5. thiophenecarboxamides according to claim 1 of formula (I), in which
R represents hydrogen or methyl,
A represents doubly linked methylene or ethylene,
Ar represents phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents:
Fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, methylsulfonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfonyl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromothiophene-2-carboxylic acid N- (4-bromophenyl) amide, 4,5-dibromothiophene-2-carboxylic acid N- (2,3-dichlorophenyl) amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide.
R für Wasserstoff oder Alkyl steht,
A für zweifach verknüpftes Alkandiyl steht,
Ar für gegebenenfalls substituiertes Aryl steht und
n für eine Zahl 0 oder 1 steht,
mit Ausnahme der Verbindungen 4,5-Dibrom-thiophen-2-carbonsäure-N-(4-brom phenyl)-amid, 4,5-Dibrom-thiophen-2-carbonsäure-N-(2,3-dichlorphenyl)-amid und 4,5-Dibrom-thiophen-2-carbonsäure-N-[2-(3,4-dimethoxyphenyl)-ethyl]--amid, dadurch gekennzeichnet, daß man Thiophencarbonsäurehalogenide der Formel (II), in welcher
Hal für Halogen steht,
mit Aminen der Formel (III),R-NH-(A)n-Ar (III)in welcher
R, A, Ar und n die oben angegebene Bedeutung haben,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Reaktionshilfsmittels umsetzt.6. Process for the preparation of thiophenecarboxamides of the formula (I), in which
R represents hydrogen or alkyl,
A represents double-linked alkanediyl,
Ar represents optionally substituted aryl and
n stands for a number 0 or 1,
with the exception of the compounds 4,5-dibromo-thiophene-2-carboxylic acid-N- (4-bromophenyl) -amide, 4,5-dibromo-thiophene-2-carboxylic acid-N- (2,3-dichlorophenyl) -amide and 4,5-dibromothiophene-2-carboxylic acid N- [2- (3,4-dimethoxyphenyl) ethyl] amide, characterized in that thiophenecarboxylic acid halides of the formula (II), in which
Hal stands for halogen,
with amines of the formula (III), R-NH- (A) n -Ar (III) in which
R, A, Ar and n have the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4233198A DE4233198A1 (en) | 1992-10-02 | 1992-10-02 | Substituted thiophenecarboxamides |
| TW082107192A TW239061B (en) | 1992-10-02 | 1993-09-03 | |
| EP93115087A EP0590458B1 (en) | 1992-10-02 | 1993-09-20 | Substituted thiophene carboxylic acid amides |
| DE59309389T DE59309389D1 (en) | 1992-10-02 | 1993-09-20 | Substituted thiophenecarboxamides |
| US08/126,821 US5369124A (en) | 1992-10-02 | 1993-09-24 | Substituted thiophenecarboxamides |
| JP5260423A JPH06220043A (en) | 1992-10-02 | 1993-09-27 | Substituted thiophenecarboxyamide |
| KR1019930019970A KR940009171A (en) | 1992-10-02 | 1993-09-27 | Substituted thiophenecarboxamides |
| BR9304104A BR9304104A (en) | 1992-10-02 | 1993-10-01 | Thiophenecarboxylic acid amides replaced process for their preparation pest control agent use and process for pest control |
| CN93118199A CN1035254C (en) | 1992-10-02 | 1993-10-02 | Substituted thiophene carboxamides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4233198A DE4233198A1 (en) | 1992-10-02 | 1992-10-02 | Substituted thiophenecarboxamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4233198A1 true DE4233198A1 (en) | 1994-04-07 |
Family
ID=6469510
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4233198A Withdrawn DE4233198A1 (en) | 1992-10-02 | 1992-10-02 | Substituted thiophenecarboxamides |
| DE59309389T Expired - Fee Related DE59309389D1 (en) | 1992-10-02 | 1993-09-20 | Substituted thiophenecarboxamides |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE59309389T Expired - Fee Related DE59309389D1 (en) | 1992-10-02 | 1993-09-20 | Substituted thiophenecarboxamides |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5369124A (en) |
| EP (1) | EP0590458B1 (en) |
| JP (1) | JPH06220043A (en) |
| KR (1) | KR940009171A (en) |
| CN (1) | CN1035254C (en) |
| BR (1) | BR9304104A (en) |
| DE (2) | DE4233198A1 (en) |
| TW (1) | TW239061B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4412333A1 (en) * | 1994-04-11 | 1995-10-12 | Bayer Ag | Microbicidal agents based on dibromo-thiophene-carboxylic acid derivatives |
| US5486621A (en) * | 1994-12-15 | 1996-01-23 | Monsanto Company | Fungicides for the control of take-all disease of plants |
| DE19642451A1 (en) * | 1996-10-15 | 1998-04-16 | Merck Patent Gmbh | Aminothiophene carboxamides |
| KR100403950B1 (en) * | 2001-04-04 | 2003-10-30 | 주식회사 엘지생명과학 | Process for preparing 5-aminomethyl-2-thiophenecarbonitrile·HCl |
| CA2595000C (en) * | 2005-01-25 | 2013-10-15 | Synta Pharmaceuticals Corp. | Thiophene compounds for inflammation and immune-related uses |
| UA106740C2 (en) * | 2009-01-30 | 2014-10-10 | Глаксосмітклайн Ллс | Crystalline n-{(1s)-2-amino-l-[(3-fluorophenyl)methyl]ethyl}-5-chloro-4-(4-chloro-l-methyl-1h-pyrazol-5-yl)-2-thiophenecarboxamide hydrochloride |
| CN106719784A (en) * | 2016-12-07 | 2017-05-31 | 河南农业大学 | Microbicide compositions and its application for preventing and treating wheat root disease |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3303201A (en) * | 1964-02-24 | 1967-02-07 | Herbert C Stecker | Halogenated anilides of thiophene carboxylic acids |
| US3243342A (en) * | 1964-02-24 | 1966-03-29 | Herbert C Stecker | Germicidal compositions containing halogenated anilides of thiophene carboxylic acids |
| DE3933573A1 (en) * | 1989-10-07 | 1991-04-18 | Basf Ag | CARBON ACID AMIDE, PROCESS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES |
| DE4011172A1 (en) * | 1990-04-06 | 1991-10-10 | Degussa | COMPOUNDS FOR CONTROLLING PLANT DISEASES |
| DE4115184A1 (en) * | 1991-05-09 | 1992-11-12 | Bayer Ag | BENZOTHIOPHEN-2-CARBOXAMID-S, S-DIOXIDE |
-
1992
- 1992-10-02 DE DE4233198A patent/DE4233198A1/en not_active Withdrawn
-
1993
- 1993-09-03 TW TW082107192A patent/TW239061B/zh active
- 1993-09-20 DE DE59309389T patent/DE59309389D1/en not_active Expired - Fee Related
- 1993-09-20 EP EP93115087A patent/EP0590458B1/en not_active Expired - Lifetime
- 1993-09-24 US US08/126,821 patent/US5369124A/en not_active Expired - Fee Related
- 1993-09-27 JP JP5260423A patent/JPH06220043A/en active Pending
- 1993-09-27 KR KR1019930019970A patent/KR940009171A/en not_active Ceased
- 1993-10-01 BR BR9304104A patent/BR9304104A/en not_active Application Discontinuation
- 1993-10-02 CN CN93118199A patent/CN1035254C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1090280A (en) | 1994-08-03 |
| BR9304104A (en) | 1994-04-05 |
| KR940009171A (en) | 1994-05-20 |
| EP0590458A1 (en) | 1994-04-06 |
| DE59309389D1 (en) | 1999-04-01 |
| CN1035254C (en) | 1997-06-25 |
| US5369124A (en) | 1994-11-29 |
| EP0590458B1 (en) | 1999-02-24 |
| TW239061B (en) | 1995-01-21 |
| JPH06220043A (en) | 1994-08-09 |
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| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |